The preparation of triflones from electrophilic triflating agents has been examined. Primary and secondary triflones are available by reaction of alkyllithium or copper organometallics with the less active electrophile, phenyltriflimide, but methyl, aryl, and vinyl triflones could not be prepared in this way. Arenes of medium reactivity can be converted to aryl triflones by Friedel-Crafts triflation with triflic anhydride and aluminum chloride.